EP0044714B1 - Process for producing mesophase pitch - Google Patents

Process for producing mesophase pitch Download PDF

Info

Publication number
EP0044714B1
EP0044714B1 EP81303276A EP81303276A EP0044714B1 EP 0044714 B1 EP0044714 B1 EP 0044714B1 EP 81303276 A EP81303276 A EP 81303276A EP 81303276 A EP81303276 A EP 81303276A EP 0044714 B1 EP0044714 B1 EP 0044714B1
Authority
EP
European Patent Office
Prior art keywords
mesophase
pitch
temperature
softening point
producing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP81303276A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0044714A2 (en
EP0044714A3 (en
Inventor
Igarashi Seiko
Izumi Takayuki
Naito Tsutomu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tonen General Sekiyu KK
Original Assignee
Toa Nenryo Kogyyo KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toa Nenryo Kogyyo KK filed Critical Toa Nenryo Kogyyo KK
Publication of EP0044714A2 publication Critical patent/EP0044714A2/en
Publication of EP0044714A3 publication Critical patent/EP0044714A3/en
Application granted granted Critical
Publication of EP0044714B1 publication Critical patent/EP0044714B1/en
Expired legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/002—Working-up pitch, asphalt, bitumen by thermal means
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues

Definitions

  • the mesophase comprises mainly molecules of a chemical structure in which polycyclic aromatic condensed rings have much more developed planar structure and orientation and in which the molecules are cohesively associated together to form a laminate of the planes.
  • the mesophase has optical properties associated with crystals and hence mesophase is considered a liquid crystal state. If mesophase pitch is spun by extrusion through a thin nozzle, the planes of the molecules are arranged nearly along the axis of the fiber. Therefore, the carbon fibers made of the mesophase pitch have a high modulus of elasticity.
  • the amount of mesophase in a pitch is determined by polarized light microscopic examination of polished samples by relating the area of the optically anisotropic portion of the total area examined. The result is expressed as volume %.
  • a pitch comprising mainly mesophase, and less than 10% non- mesophase, is called "mesophase pitch" herein.
  • the thermal cracking/polycondensation reaction of the heavy hydrocarbons is carried out substantially in a simple step at a temperature of about 400°C over a long period of time. Therefore, as the mesophase content is increased gradually, the softening point of the pitch as a whole is elevated and, accordingly, temperature suitable for the melt spinning thereof (spinning temperature) is also elevated.
  • the principal object of the present invention is to provide a process for producing a mesophase pitch wherein the whole steps can be completed in a short time of, for example, 1-3 hours without necessitating complicated steps of high temperature filtration of infusible matter, extraction with a solvent and addition and removal of a catalyst.
  • Another object of the present invention is to provide a process for producing a mesophase pitch having a mesophase content of 90%-100% and a low softening point (for example, 260°C) and, therefore, a low optimum spinning temperature (for example, 340°C).
  • Still another object of the present invention is to provide a process for producing mesophase pitch which does not substantially form any decomposition gases or infusible matter during the spinning, thereby producing pitch fibers scarecely containing bubbles or solid contaminants, and hence providing carbon fibers of a high strength.
  • Another object of the present invention is to provide a process for producing a mesophase pitch wherein properties and quality of the pitch can be controlled stably and easily by providing steps of accumulation again, and separation of the liquid crystalline pitch after the thermal cracking/polycondensation reaction step, even if properties of the starting material vary considerably, or even if the operation conditions in the preceding step are varied to some extent.
  • Figures 1 through 5 are microphotographs at magnifications of 50x of polished pitch sections which were taken by means of a polarized light microscope of reflection type under crossed polarizers.
  • One of the characteristic features of the present invention is that various carbonaceous substances such as heavy hydrocarbon oil, tar and pitch can be used as the starting material as described above. More particularly, there may be used various petroleum heavy oils, tar obtained by the thermal cracking, and tar obtained by the catalytic cracking as well as heavy oil, tar and pitch obtained by the dry distillation of coal and, in addition, heavy liquefied coal obtained in the liquefaction of coal.
  • various carbonaceous hydrocarbons containing solid particles, such as carbon particles are not preferred starting materials without previously removing such carbon particles through a suitable filter. Also, materials containing an excess of light oil fraction are not preferred starting materials.
  • They can, of course, be used as the starting material of the present invention after removing the harmful components by any method.
  • they may be used in the present invention after treatment by (1) the removal of insoluble matter with a suitable solvent after slight, previous polymerization reaction, or (2) hydrocracking reaction or (3) heat- soaking followed by highly reduced pressure distillation for the removal of the bottom residue.
  • the reaction can be carried out in a short period of time of, for example, only one hour at a high temperature of 440°C.
  • This is one of the characteristic features of the present invention.
  • it is unsuitable to carry out the thermal cracking/polycondensation reaction at a temperature of above 460°C, since the evaporation of the unreacted starting material is accelerated, the softening point of the mesophase is elevated and the control of the reaction becomes difficult.
  • the reaction system is stirred so as to prevent the local overheating.
  • the thermal cracking/polycondensation reaction can be carried out under reduced pressure so as to remove the low molecular weight substances formed by the thermal cracking or preferably while an inert gas is introduced in the reactor, though it is not necessary and merely optional to bubble the gas through the pitch.
  • the thermal cracking/polycondensation reaction can be carried out under atmospheric or elevated pressure without the inert gas introduction and then, the low molecular weight substances can be removed by reduced pressure distillation or by stripping treatment with an inert gas.
  • Another important feature of the present invention is that the thermal cracking/polycondensation reaction is suspended when a mesophase content in the resulting pitch, from which the low molecular weight products and unreacted reactants have substantially been removed, of 20-80%, preferably 40-70%, and more preferably 40-60% has been attained, and then the pitch is transferred into the aging/settling and separation steps where the mesophase is allowed to grow, precipitate, accumulate, age, and separate.
  • the above aging/settling/separation step is an important characteristic feature of the present invention.
  • the temperature employed in this step is preferably in a range slightly below the temperature range of the preceding thermal cracking/polycondensation step. More particularly, said step must be carried out at a sufficiently low temperature at which the thermally cracked gas generation is small, no more polycondensation reaction proceeds and molecular weight increase of the already formed mesophase molecules hardly occurs, but a sufficiently high temperature at which such a viscosity can be kept as that the whole system is liquid and the growing, coalescence and sedimentation of mesophase occur rapidly. Such a temperature range varies depending on the starting material and thermal cracking/polycondensation conditions in the preceding step.
  • a latitude of several ten degrees centigrade is allowed in this step and, accordingly, the temperature can be controlled within a broad range.
  • the normal temperature range in this step is from 350°C to not above 400°C, generally preferably in the range 360°-390°C.
  • the temperature is generally maintained within such a range by slightly warming or cooling the pitch which has been heated to the high temperature in the preceding step, and particular control with a large heat is unnecessary.
  • the object can be attained substantially by allowing the mixture to stand without stirring of the liquid phase of the pitch.
  • slow stirring or slow circulation of the mixture can be applied continuously in the course of the reaction.
  • the mesophase formed in the preceding thermal treatment step is generally dispersed in the pitch as spheres having a diameter of up to 200 ⁇ (see Figure 1). Those spheres grow and are coalesced gradually in this step and accumulate at the bottom of the mixture. These coalesced spheres are further coalesced to form large masses at the bottom (see Figure 2). Then, the masses are coalesced to form a large liquid layer (see Figure 3), which finally is divided from the upper non-mesophase pitch (containing a small amount of the very small mesophase spheres) by a clear, plane boundary ( Figure 4).
  • the mesophase pitch may be drawn out when the spheres of the mesophase have settled sufficiently, but have not completely coalesced in a clearly divided lower layer (see Figures 2 and 3).
  • the upper layer mainly comprising the non-mesophase portion from the aging/settling/separation step can be returned and used again in the aging/settling/separation step or in the preceding thermal cracking/polycondensation step. More particularly, it has been found that if the upper layer, mainly comprising the non-mesophase and still containing a very small amount of the fine spheres (diameter: 10-20 p), is subjected again to the aging/settling/separation step after the separation of the lower layer; the spheres of the mesophase grow, settle and coalesce to form the mesophase settling in a lower layer, though yield thereof is a little lower than that obtained in the first aging/settling/separation.
  • the mesophase content thereof is increased in a short period of time and the mesophase spheres grow into greater diameters. Then, they are transferred into the aging/settling/separation step to separate out the lower layer, thereby obtaining the substantially homogeneous mesophase pitch of low softening point with a high yield.
  • the present invention includes a process wherein the upper layer, mainly comprising the non-mesophase pitch from the aging/settling/separation step, is recycled to obtain the substantially homogeneous mesophase pitch of a low softening point with a high yield.
  • a pitch produced by the process of the present invention can have a mesophase content of 90% to 100% and is a substantially homogeneous mesophase pitch. In addition, it can have an extremely low softening point (230°C to 320°C) which could not be attained easily in the prior art.
  • the pitch has, normally, a sufficiently low melt spinning temperature (280°C to 380 0 C); and, it has been found that carbon fibers of extremely good performance can be obtained stably from the pitch of this invention.
  • the pitch fibers thus obtained from the substantially homogeneous mesophase of the low softening point formed by the present invention are completely made infusible by heating to a temperature above 200°C for a time ranging from about 10 minutes to about one hour under oxygen atmosphere.
  • the pitch fibers thus made infusible are carbonized by heating the same to 1,300°C in an inert gas.
  • resulting carbon fibers have a tensile strength of 2.0-3.8x 1 09 Pa and tensile modulus of elasticity of 1.6-3.Ox 10" Pa, though the properties vary depending on diameters thereof.
  • the carbon fibers were carbonized up to 1,500°C, the tensile strength and tensile modulus of elasticity thereof were 2.4 ⁇ 4.0x10 9 Pa and 2.0 ⁇ 4.0x10 11 Pa, respectively.
  • the pitch in the upper layer had a softening point of 192°C, specific gravity of 1.30 and quinoline-insoluble matter content of 4 wt.%.
  • the pitch in the lower layer comprised 100% mesophase of large flow patterns having a softening point of 256°C, specific gravity of 1.35 and quinoline-insoluble matter content of 41 wt.%. Yield of the nonmesophase pitch in the upper layer was 64.5 wt.% based on the material charged and yield of the 100% mesophase pitch in the lower layer was 35 wt.%. (The lower layer pitch was used in Example 6).
  • Example 2 For comparison, 1,000 g of the same starting tar as in Example 1 was heat-treated at 430°C in the same device as in Example 1 for 3 hours under nitrogen gas stream at atmospheric pressure with stirring to obtain 8.8 wt.%, based on the starting tar, of 100% mesophase pitch by only the heat treatment.
  • the pitch was observed by means of a polarized light microscope to reveal that it comprised large flow pattern portions and small flow pattern portions and had a softening point of 325°C, specific gravity of 1.37 and quinoline-insoluble matter content of 62 wt.%. This product was also used in Example 6 for comparison.
  • the upper layer comprised non-mesophase pitch containing about 25% of the mesophase spheres having diameters of up to 20 ⁇ .
  • the upper layer pitch had a softening point of 176°C, specific gravity of 1.31, quinoline-insoluble matter content of 4 wt.%, carbon content of 93.4 wt.% and hydrogen content of 4.9 wt.%.
  • the boundary pitch was the heterogeneous pitch in which the non-. mesophase containing the mesophase globules of diameters of up to 100 ⁇ in the mother layer and the bulky mesophase were intermixed to form a complicated structure.
  • the lower layer pitch comprised 100% mesophase having large flow patterns, a softening point of 260°C, specific gravity of 1.35, quinoline-insoluble matter content of 43 wt.%, carbon content of 94.1 wt.% and hydrogen content of 4.6 wt.%.
  • a tarry substance obtained by cracking coal into liquid was distilled under reduced pressure until a temperature of 400°C (calculated under atmospheric pressure) was attained.
  • the distillation residue was used as the starting material.
  • the starting material had a carbon content of 91.6 wt.%, hydrogen content of 6.7 wt.%, specific gravity of 1.13 and quinoline-insoluble matter content of 0 wt.%.
  • the starting material was heat-treated at 440°C for 2 hours in the same manner as in Example 1 and the resulted pitch was observed by means of a polarized light microscope to reveal that it contained about 40% of mesophase spheres of diameters of up to 200 jM which were perfectly spherical, and it had a softening point of 187°C, specific gravity of 1.32 and a quinoline-insoluble matter content of 11 wt.% with a yield of 32 wt.% based on the residual oil used as the starting material.
  • the pitch was allowed to stand at 380°C for 0.5 hours in the same manner as in Example 1 and then observed by means of a polarized light microscope to reveal that the upper layer comprised a non-mesophase containing about 20% of perfectly spherical mesophase spheres having a diameter of up to 20 p and having a softening point of 176°C; specific gravity of 1.29 and quinoline-insoluble matter content of 3 wt.%.
  • the lower layer comprised 100% mesophase pitch of a large flow structure having a softening point of 265°C, specific gravity of 1.36 and quinoline-insoluble matter content of 48 wt.%.
  • a pitch produced in the same manner of heat-treatment as in Example 1 was charged in small aluminum vessels and allowed to stand at various temperatures in the range of from 350°C to 400°C and during various hours under nitrogen atmosphere.
  • the pitches were polished in the perpendicular direction as they were kept in the vessels.
  • the cross sections thereof were observed by means of a polarized light microscope. Then, softening points of the upper and lower layers were measured to obtain the results shown in Table 2.
  • the pitch produced for the comparison with that obtained in Example 1 had a high spinning temperature of at least 390°C. It could not be spun at a rate of 500 m/min. At a rate of even 300 m/min., the breakage frequency of the fiber was high and the resulting carbon fiber had an insufficient strength.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Textile Engineering (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Inorganic Fibers (AREA)
EP81303276A 1980-07-21 1981-07-16 Process for producing mesophase pitch Expired EP0044714B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP99646/80 1980-07-21
JP55099646A JPS57119984A (en) 1980-07-21 1980-07-21 Preparation of meso-phase pitch

Publications (3)

Publication Number Publication Date
EP0044714A2 EP0044714A2 (en) 1982-01-27
EP0044714A3 EP0044714A3 (en) 1982-03-31
EP0044714B1 true EP0044714B1 (en) 1984-06-13

Family

ID=14252811

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81303276A Expired EP0044714B1 (en) 1980-07-21 1981-07-16 Process for producing mesophase pitch

Country Status (6)

Country Link
US (2) US4533461A (enrdf_load_stackoverflow)
EP (1) EP0044714B1 (enrdf_load_stackoverflow)
JP (1) JPS57119984A (enrdf_load_stackoverflow)
AU (1) AU543419B2 (enrdf_load_stackoverflow)
CA (1) CA1164384A (enrdf_load_stackoverflow)
DE (1) DE3164153D1 (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3829986A1 (de) * 1988-09-03 1990-03-15 Enka Ag Verfahren zur erhoehung des mesophasenanteils in pech

Families Citing this family (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5834569B2 (ja) * 1980-09-02 1983-07-27 興亜石油株式会社 炭素繊維の製造法
JPS5777615A (en) * 1980-10-31 1982-05-15 Ogata Kikai Seisakusho:Kk Automatic machine for manufacturing incense stick
JPS5778486A (en) * 1980-11-05 1982-05-17 Nippon Steel Chem Co Ltd Preparation of meso-phase pitch
JPS5788016A (en) * 1980-11-19 1982-06-01 Toa Nenryo Kogyo Kk Optically anisotropic carbonaceous pitch for carbon material, its manufacture, and manufacture of carbonaceous pitch fiber and carbon fiber
JPS5930192B2 (ja) * 1980-12-15 1984-07-25 富士スタンダ−ドリサ−チ株式会社 潜在的異方性ピツチ
US4655902A (en) * 1981-08-28 1987-04-07 Toa Nenryo Kogyo Kabushiki Kaisha Optically anisotropic carbonaceous pitch
JPS58101191A (ja) * 1981-12-10 1983-06-16 Idemitsu Kosan Co Ltd メソ相ピツチおよび該ピツチ系炭素繊維の製造方法
JPS58134180A (ja) * 1982-02-04 1983-08-10 Kashima Sekiyu Kk メソフエ−ズピツチの改良製造法
JPS58142976A (ja) * 1982-02-22 1983-08-25 Toa Nenryo Kogyo Kk 均質低軟化点光学的異方性ピッチの製法
JPS58164687A (ja) * 1982-03-24 1983-09-29 Toa Nenryo Kogyo Kk 光学的異方性ピツチの製造方法
JPS58168687A (ja) * 1982-03-31 1983-10-05 Toa Nenryo Kogyo Kk 光学的異方性ピツチの連続的製造方法
EP0117099A3 (en) * 1983-02-08 1985-04-17 Fuji Standard Research Inc. Novel carbonaceous pitch, process for the preparation thereof and use thereof to make carbon fibers
JPS59163422A (ja) * 1983-03-09 1984-09-14 Kashima Sekiyu Kk 石油系メソフエ−ズの紡糸法
JPS59163424A (ja) * 1983-03-09 1984-09-14 Kashima Sekiyu Kk 石油系メソフエ−ズの紡糸法
US4913889A (en) * 1983-03-09 1990-04-03 Kashima Oil Company High strength high modulus carbon fibers
US4487685A (en) * 1983-06-24 1984-12-11 Kashima Oil Company Limited Method for producing mesophase-containing pitch by using carrier gas
US4529498A (en) * 1983-06-24 1985-07-16 Kashima Oil Company Limited Method for producing mesophase pitch
US4512874A (en) * 1983-06-24 1985-04-23 Kashima Oil Company Limited Method for producing mesophase continuously
US4529499A (en) * 1983-06-24 1985-07-16 Kashima Oil Company Limited Method for producing mesophase pitch
JPS6034619A (ja) * 1983-07-29 1985-02-22 Toa Nenryo Kogyo Kk 炭素繊維及び黒鉛繊維の製造方法
JPS6049085A (ja) * 1983-08-29 1985-03-18 Osaka Gas Co Ltd コ−ルタ−ル又はコ−ルタ−ルピツチの処理方法
JPS61241392A (ja) * 1985-12-26 1986-10-27 Toa Nenryo Kogyo Kk メソ相ピツチの製造方法
JPS61241390A (ja) * 1985-12-26 1986-10-27 Toa Nenryo Kogyo Kk メソ相ピツチの製造方法
JPS62270685A (ja) * 1986-05-19 1987-11-25 Maruzen Petrochem Co Ltd メソフェ−ズピッチの製造法
AU593326B2 (en) * 1986-06-09 1990-02-08 Conoco Inc. Pressure settling of mesophase
CA1302934C (en) * 1987-06-18 1992-06-09 Masatoshi Tsuchitani Process for preparing pitches
US4891126A (en) * 1987-11-27 1990-01-02 Mitsubishi Gas Chemical Company, Inc. Mesophase pitch for use in the making of carbon materials and process for producing the same
US5182010A (en) * 1989-11-29 1993-01-26 Mitsubishi Gas Chemical Company, Inc. Mesophase pitch for use in the making of carbon materials
US5730949A (en) * 1990-06-04 1998-03-24 Conoco Inc. Direct process route to organometallic containing pitches for spinning into pitch carbon fibers
US5437780A (en) * 1993-10-12 1995-08-01 Conoco Inc. Process for making solvated mesophase pitch
ATE257277T1 (de) 2000-10-31 2004-01-15 Sez Ag Vorrichtung zur flüssigkeitsbehandlung von scheibenförmigen gegenständen
US7067050B2 (en) * 2002-11-14 2006-06-27 Marathon Ashland Petroleum Llc Petroleum hydrocarbon binder with reduced polycyclic aromatic hydrocarbon content
US8202480B2 (en) * 2009-06-25 2012-06-19 Uop Llc Apparatus for separating pitch from slurry hydrocracked vacuum gas oil
US8231775B2 (en) 2009-06-25 2012-07-31 Uop Llc Pitch composition
US8540870B2 (en) 2009-06-25 2013-09-24 Uop Llc Process for separating pitch from slurry hydrocracked vacuum gas oil
US9150470B2 (en) 2012-02-02 2015-10-06 Uop Llc Process for contacting one or more contaminated hydrocarbons
CN108795465A (zh) * 2013-12-13 2018-11-13 陈德桂 一种沥青的制备方法
WO2016019443A1 (pt) * 2014-08-05 2016-02-11 Petróleo Brasileiro S.A. - Petrobras Processo para a produção de piche de petróleo mesofásico fiável visando a produção de fibras de carbono contínuas
US10167913B2 (en) * 2015-04-29 2019-01-01 Goodrich Corporation High performance carbon fiber
CN107601492B (zh) * 2017-10-17 2020-06-30 北京君研碳极科技有限公司 一种二维类石墨结构材料的制备方法
CN113088327B (zh) * 2019-12-23 2022-09-09 中国石油化工股份有限公司 一种生产中间相沥青的方法
US11401470B2 (en) * 2020-05-19 2022-08-02 Saudi Arabian Oil Company Production of petroleum pitch
EP4164984A4 (en) 2020-06-12 2024-12-04 Carbon Holdings Intellectual Properties, LLC COAL PROCESSING SYSTEMS AND METHODS FOR USE IN A DIRECT AIR CAPTURE SYSTEM
CN114479896B (zh) * 2020-10-26 2023-04-25 中国石油天然气股份有限公司 一种分离石油沥青组分的方法
US11898101B2 (en) 2021-08-26 2024-02-13 Koppers Delaware, Inc. Method and apparatus for continuous production of mesophase pitch

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2896261A (en) * 1954-12-27 1959-07-28 Gulf Research Development Co Method of cooling and granulating petroleum pitch
US3812240A (en) * 1970-04-06 1974-05-21 Great Lakes Carbon Corp Production of highly ordered graphite particles
US4032490A (en) * 1974-11-15 1977-06-28 Sumitomo Durez Company, Ltd. Wax compositions for flame retardant electrical insulation coatings
US3976729A (en) * 1973-12-11 1976-08-24 Union Carbide Corporation Process for producing carbon fibers from mesophase pitch
US4026788A (en) * 1973-12-11 1977-05-31 Union Carbide Corporation Process for producing mesophase pitch
JPS50118028A (enrdf_load_stackoverflow) * 1974-03-04 1975-09-16
US4033430A (en) * 1976-06-09 1977-07-05 The Raymond Lee Organization, Inc. Speaker enclosure
JPS5842708B2 (ja) * 1977-06-07 1983-09-21 松下電器産業株式会社 電動機
US4184942A (en) * 1978-05-05 1980-01-22 Exxon Research & Engineering Co. Neomesophase formation
JPS5854081B2 (ja) * 1980-01-04 1983-12-02 興亜石油株式会社 メソカ−ボンマイクロビ−ズの製造法
JPS5917044B2 (ja) * 1981-06-01 1984-04-19 興亜石油株式会社 晶質化物質の製造方法および装置
JPS58134181A (ja) * 1982-02-04 1983-08-10 Kashima Sekiyu Kk メソフエ−ズの連続製造法
JPS58134179A (ja) * 1982-02-04 1983-08-10 Kashima Sekiyu Kk メソフエ−ズピツチの製造法
US4529498A (en) * 1983-06-24 1985-07-16 Kashima Oil Company Limited Method for producing mesophase pitch

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3829986A1 (de) * 1988-09-03 1990-03-15 Enka Ag Verfahren zur erhoehung des mesophasenanteils in pech

Also Published As

Publication number Publication date
AU7312381A (en) 1982-01-28
JPS57119984A (en) 1982-07-26
EP0044714A2 (en) 1982-01-27
CA1164384A (en) 1984-03-27
AU543419B2 (en) 1985-04-18
USRE32792E (en) 1988-11-29
US4533461A (en) 1985-08-06
DE3164153D1 (en) 1984-07-19
JPS6138755B2 (enrdf_load_stackoverflow) 1986-08-30
EP0044714A3 (en) 1982-03-31

Similar Documents

Publication Publication Date Title
EP0044714B1 (en) Process for producing mesophase pitch
US4454019A (en) Process for producing optically anisotropic carbonaceous pitch
EP0034410B1 (en) Process for the preparation of a feedstock for carbon artifact manufacture
US4454020A (en) Process for producing a homogeneous low softening point, optically anisotropic pitch
US4601813A (en) Process for producing optically anisotropic carbonaceous pitch
EP0055024B1 (en) Carbonaceous pitch, production thereof and carbon fibers therefrom
JPS5845277A (ja) 光学的異方性炭素質ピツチおよびその製造方法
US4655902A (en) Optically anisotropic carbonaceous pitch
EP0089840B1 (en) Process for producing an optically anisotropic carbonaceous pitch
JPS6224036B2 (enrdf_load_stackoverflow)
US4810437A (en) Process for manufacturing carbon fiber and graphite fiber
JPH01247487A (ja) メソフェースピッチの製造方法
JPH0415274B2 (enrdf_load_stackoverflow)
JPS6250515B2 (enrdf_load_stackoverflow)
EP0430689A1 (en) Mesophase pitch for use in the making of carbon materials
JPH03167291A (ja) 光学的異方性ピッチ及びその製造方法
JPS6250514B2 (enrdf_load_stackoverflow)
JPH01254797A (ja) メソフェースピッチの製造方法
JPH01249887A (ja) メソフェースピッチの製造方法
JPH01207385A (ja) メソフェースピッチの連続的製造方法
JPH01268788A (ja) 炭素繊維用メソフェースピッチの製造方法
JPS6250513B2 (enrdf_load_stackoverflow)
JPS6250516B2 (enrdf_load_stackoverflow)
JPH032298A (ja) メソフェースピッチの製造方法
JPS58196293A (ja) 光学的異方性ピツチの製造方法及び製造用原料

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE DE FR GB IT NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Designated state(s): BE DE FR GB IT NL

17P Request for examination filed

Effective date: 19820825

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR GB IT NL

REF Corresponds to:

Ref document number: 3164153

Country of ref document: DE

Date of ref document: 19840719

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19900731

Year of fee payment: 10

Ref country code: BE

Payment date: 19900731

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19910731

BERE Be: lapsed

Owner name: TOA NENRYO KOGYO K.K.

Effective date: 19910731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19920201

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19940706

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19940708

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19940711

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19950716

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19950716

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19960402

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19960430

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST